Compounds of copper, arsenic, and a sulphmonocarboxylic acid and process of making them



Patented May 23, 1939 PATENT" OFFICE COMPOUNDS OF COPPER, ARSENIC, AND A SULPHMONOCARBOXYLIC ACID AND w PROCESS OF MAKING THEM Frederick E. Dearborn, Washington, D. (2.; dedicated to the free use of the People of the United States of America No Drawing. Application January 28, 1938, Serial No. 187,574

7 Claims.

(Granted under the act of March 3, 1883, as

amended April 30, 1928; 370 0. G. 757) This application is made under the .act approved March 3, 1883, as amended by the act of April 30, 1928, and the invention hereindescribed, if patented, may be manufactured and used by or for the Government of the United States of America for governmentalpurposes without the paymentto meof any royalty thereon.

I hereby dedicate the invention. herein described to the free use of the People of the United 10 States of. America to take effect on the granting of apatent to me.

This invention embraces a new compound or compounds, having the composition hereinafter specifically set forth and the mode or process of manufacturing the same which will be hereinafter fully described. It is to be understood, however, that changes may be made in such composition of matter and in the step or steps relating: thereto, within the scope of the appended claims, without departing from the spirit of the invention.

I have found that a complex compound or compounds can be prepared containing arsenic, copper, and a sulph-monocarboxylic acid of the general formula CnH21t-2S02. The compound or compounds are greenish in color and are suitable for insecticidal and fungicidal uses. They differ in composition from the compounds defined by United States Patent 2,080,004 in that the element sulphur has been introduced into the molecule, imparting different chemical and physical properties to them. They are practically insoluble in water, and when dry are not wet by it without the use of a wetting agent.

As indicated the principal and poisonous ingredient in my new insecticide or insecticides comprises-mainly a complex compound composed of copper meta-arsenite united with a copper salt of a'sulphmonocarboxylic acid of the gen- 40 eral formula CnH2n-2SO2, for example copper sulph-crotoarsenite of probable formula theoretically containing 52.53 percent arsenious oxide (AS203) 28.16 percent copper oxide (CuO), and 19.31 percent sulph-crotonic anhydride.

In carrying out my invention I first prepare the sulph-unsaturated fatty acid by heating a fatty acid of series CnHZn-ZOZ or its glyceride with sulphur at a temperature ranging from 160-210 C. or higher, until the sulphur has combined with the unsaturated fatty acid. The addition of a small amount of iodine as a catalyst hastens the reaction which is sometimes very vigorous with evolution of considerable heat. This is especially true contain one double bond and are capable of 5 adding one atom of sulphur to form the new acid series CnHZn-ZSO2- The acids below oleic are heated with sulphur in sealed vessels to prevent the escape of reactants. Applications for patent, Serial Nos. 125,273, 125,274, and 125,275 have 10 been made covering the sulph-unsaturated fatty acids, their sulph-glycerides and the process of making the same. The sulph-fatty acids or their sulph-glycerides retain some unreacted sulphur as an impurity. This may be removed by boiling 15 with a solution of an alkali metal salt, converting the sulph-acids or sulph-glycerides into the alkali metal salt, producing a soap. The soap may be salted out of solution, removed and further purified, or the original soap solution used in 20 preparing my new compounds. The insecticide prepared from the unpurified soap will contain some copper sulphide and possibly other insoluble sulphides as impurities. In preparing the sulph-unsaturated fatty acids, the free acid or 25 a vegetable, animal or fish oil containing appreciable amounts of unsaturated acids of series CnH2n-202 may be used.

To the boiling solution of the alkali metal salt of a sulph-acid is added a hot solution of an alkali metal arsenite, any excess alkali is neutralized with a dilute mineral acid, such as H2804, and then a solution of a soluble copper salt, such as CuSO4 or CuClz is added with vigorous agitation. When all of the copper salt has been added, the mixture should be neutral or very faintly acid in reaction, if not, it is made so by the addition of dilute alkali or mineral acid. The mixture is now boiled for half an hour or longer to cause complete reaction and granulation of the com- 40 pound. Before filtering it is better to make the mixture slightly acid by adding dilute HzSO-g to dissolve any unreacted copper arsenite that may be present. It is preferable to allow the reacted mixture to stand until cold with occasional agi- 45 tation, when it is filtered and well washed to remove soluble impurities, and then dried.

The proportions of copper, arsenic, and sulphmonocarboxylic acid salts to be mixed may be calculated from the formula 3CuAszO4.CuOR, in 50 which R represents the sulph-monocarboxylic anhydride. For example, the following are given as illustrations:

(a) Copper sulph-acrylicoarsenite of probable formula 3CuAs2O4.CuCeHsS2O4, theoretically con- 55 taining 57.19 per cent arsenious oxide (AS203). 30.66 percent copper oxide (CuO) and 12.15 percent sulph-acrylic anhydride. To produce 100 grams of the compound the following weights of materials are required:

Grams Sodium arsenite (Na2HASO3) 98.1 Copper sulphate (CuSO4.5HzO) 96.3 Sodium sulph-acrylate 1 18.3

(b) Copper sulf-oleoarsenite of probable formula 3C11AS204.CUC36H66S204, theoretically containing 38.99 percent arsenious oxide (AS203), 20.83 percent copper oxide (CuO) and 40.18 percent sulf-oleic anhydride. To produce 100 grams of the compound the following weights of materials are required:

Grams Potassium arsenite (KASO2) 57.6 Cupric chloride (CuClz.2H2O) 44.7 Sodium sulf-oleate 72.9

(0) Copper sulph-erucoarsenite of probable formula 3CuAs2O4.CuC44HszS2O4, theoretically containing 36.32 percent arsenious oxide (AS203), 19.47 percent copper oxide (CuO), and 44.211percent sulph-erucic anhydride. To produce grams of the compound the following weights of materials are required:

V Grams Arsenious oxide (AS203) 36.4 Sodium hydroxide (NaOH) 29.4 Copper sulphate (CuSOrfiHzO) 61.1 Sodium sulph-eruciate 81.4

Having thus described my invention, I claim: 1. A new compound of the general formula BCuAszOaCuOR in which R is the anhydride of a sulph-monocarboxylic acid of the general formula CnH2n-2SO2.

2 A new insecticide and fungicide consisting of the complex product of the reaction between a solution of an inorganic soluble copper salt, an alkali metal arsenite, and an alkali metal salt of the sulph-monocarboxylic acids of the general formula CnH21i-2SO2.

. .3. A new compound of the general formula 3CuAszO4.CuOR, in which R is the anhydride of sulph-acrylic acid.

4. A new compound of the general formula 3CuAszO4.CuOR, in which R is the anhydride of sulph-oleic acid.

of the general formula CnH2n-2SO2 containing from 3 to 22 carbon atoms in its molecule; which comprises bringing together a solution of alkali metalarsenite, a solution of a water soluble inorganic cupric salt, and a solution of an alkali metal salt of a sulph-monocarboxylic acid of the general formula CnH2n2SO2 containing from 3 to 22 carbon atoms in its molecule obtained by 'saponifying an oil containing glycerides of CnH2n202 series of acids in which one atom of sulphur has been added to the unsaturated acid radical by heating with sulphur from to 210 C.; heating and agitating the mixture until the reactions have been completed, washing and drying the product.

FREDERICK E. DEARBORN. 

